CN102769122B - Method for preparing electrode plate of lithium ion battery - Google Patents
Method for preparing electrode plate of lithium ion battery Download PDFInfo
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- CN102769122B CN102769122B CN201210273175.0A CN201210273175A CN102769122B CN 102769122 B CN102769122 B CN 102769122B CN 201210273175 A CN201210273175 A CN 201210273175A CN 102769122 B CN102769122 B CN 102769122B
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- lithium ion
- ion battery
- nano
- aluminium foil
- electrode piece
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 238000005530 etching Methods 0.000 claims abstract description 20
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000005030 aluminium foil Substances 0.000 claims description 40
- 239000011230 binding agent Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 239000011852 carbon nanoparticle Substances 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 6
- 229910052782 aluminium Inorganic materials 0.000 abstract 6
- 239000011888 foil Substances 0.000 abstract 6
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 235000019241 carbon black Nutrition 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a method for preparing an electrode plate of a lithium ion battery, comprising the following steps of: 1) providing an aluminum foil and etching a groove in the surface of the aluminum foil by using oxidizing acid, wherein the thickness of the groove is 0.1-1mum, and the surface density of the etched aluminum foil is 60-85g/m <2>; and 2) coating a layer of nano-carbon coating on the surface with the etched groove of the aluminum foil to obtain the electrode plate of the lithium ion battery, wherein the thickness of the nano-carbon coating is 1-5mum. By adopting the technical solution of etching the aluminum foil and coating the nano-carbon coating, the contact area of an active material and a nano-prime coating is increased and the adhesive force between the nano-carbon coating and the aluminum foil is enhanced, therefore, the internal resistance of the battery during the charge-discharge of the battery can be reduced, the polarization of the battery decreased, and the heat dispersion of the electrode plate is improved.
Description
Technical field
The preparation method who the present invention relates to a kind of lithium ion battery electrode piece, belongs to technical field of lithium ion.
Background technology
Ferric phosphate lithium cell is a kind of novel energy-storing lithium ion battery growing up in recent years, and, environmental protection cheap with it, has extended cycle life and be subject to the favor in market.And because battery in use can produce a large amount of heats, affect cycle life and the safety of its battery, especially larger on the impact of high capacity cell.Although be to reduce the heat that battery produces at present, adopt provided with fan on battery rack to get rid of heat, these methods are the surperficial heat that has reduced battery just, does not produce heat from basic solution battery.The heat producing due to battery be mainly due to electric current by time, the heat that resistance heating produces, is to reduce the heat that resistance produces, and can reduce on the one hand the resistance of battery, reduces on the other hand the distance of ion transfer; Therefore how dwindling cell resistance and reducing ion transfer distance becomes and in lithium ion battery, is difficult to the technical barrier that overcomes.
Summary of the invention
The object of this invention is to provide a kind of preparation method of lithium ion battery electrode piece, to reduce the resistance of lithium ion battery, improve the heat dispersion of lithium ion battery.
In order to realize above object, the technical solution adopted in the present invention is: a kind of preparation method of lithium ion battery electrode piece, comprises the following steps:
1) get aluminium foil, adopt oxidizing acid to etch the groove that thickness is 0.1～1 μ m on aluminium foil surface, after etching, the surface density of aluminium foil is 60～85g/m2;
2) in surface-coated one deck nano-sized carbon coating of aluminium foil etched recesses, make lithium ion battery electrode piece, the thickness of this Nano carbon coating is 1～5 μ m.
Described groove is horizontal or longitudinal extension along aluminium foil, and its width of rebate is 0.1～10mm.
Described in step 1), oxidizing acid is nitric acid or sulfuric acid.
Described nano-sized carbon coating comprises carbon nano-particles.
Step 2) coating of described nano-sized carbon coating adopts with the following method: 140～500 parts of aqueous binders, 800～1500 parts of redistilled water mixing and stirring are obtained to binder system, under ultrasonic wave dispersion condition, in binder system, add 45～65 parts of carbon nano-particles, after adding, continue ultrasonic wave and disperse within 1～5 hour, to obtain coating liquid, this coating liquid is coated in uniformly to the surface of aluminium foil etched recesses.
Described carbon nano-particle divides three times and adds above, and the time interval adding is 30～60 minutes.
Described carbon nano-particles be one or both in carbon black, Supper P arbitrarily than mixing, the granularity of described carbon nano-particles is 1～100nm.
Described aqueous binders is that one or both of polypropylene, poly-propionic acid are arbitrarily than mixing.
The surface that coating liquid is coated in aluminium foil etched recesses uniformly adopts intaglio printing technology to apply.
Because lithium ion battery can produce a large amount of heat in high rate charge-discharge process, affect its electrolyte and stability of material, also can cause battery temperature skewness simultaneously, affect the cycle life of battery.The present invention is by adopting the technical scheme of etching aluminium foil and nano-sized carbon coating, increase the contact area of active material and nanometer priming coat, improved the adhesion of nano-sized carbon coating and aluminium foil simultaneously, thereby battery internal resistance of cell in charge and discharge process is reduced, and battery polarization reduces, improves the heat dispersion of pole piece.
Brief description of the drawings
Fig. 1 is the adhesion curve chart of embodiment 1 and comparative example electrode plates;
Fig. 2 is the temperature rise curve figure of embodiment 1 lithium ion battery;
Fig. 3 is the temperature rise curve figure of embodiment 1 comparative example lithium ion battery;
Fig. 4 is the multiplying power discharging curve chart of embodiment 1 lithium ion battery;
Fig. 5 is the multiplying power discharging curve chart of embodiment 1 comparative example lithium ion battery.
Embodiment
Embodiment 1
The preparation method of the lithium ion battery electrode piece of the present embodiment, comprises the steps:
1) by red fuming nitric acid (RFNA) etching aluminium foil, make its aluminium foil etch the etching aluminium foil that groove thickness is 1 μ m, groove is along the horizontal expansion of aluminium foil, and the width of rebate of groove is 1mm, and etching aluminium foil surface density is 60g/m
2;
2) take 280 grams of aqueous binders A (binding agent is LA132 aqueous binders, Chengdu Yindile Power Source Science and Technology Co., Ltd produce), 1125 grams of second distillation aqueous solvents, carry out mechanical agitation 2 hours, obtain homogeneous, stable binder system; Under ultrasonic wave dispersion condition, divide and added powder nanometer conductive carbon combined conductive agent one time every 30 minutes three times, its conductive nano carbon combined conductive agent is 46.87 grams of nano carbon blacks (granularity 5nm) and 9.38 grams of Supper P combined conductive agent (granularity 5nm; Producer: Te Migao company of Switzerland produces) composition, after adding, disperse 2 hours at ultrasonic echography again, finally obtain coating liquid, the viscosity of coating liquid is 8000mPas; Adopt afterwards intaglio printing technology that coating liquid is coated on etching aluminium foil, coating thickness is 2 μ m, after being dried, obtains lithium ion battery electrode piece.
Adopt the lithium ion battery electrode piece of the present embodiment to be prepared into lithium ion battery: anodal LiFePO4 slurry is obtained to anode pole piece A by coating machine upper coating of electrode plates (being coated with cated one side) of the present embodiment, preparing battery core length by roll squeezer, slicing machine, laminating machine is afterwards 165 millimeters, and wide is that 80 millimeters, thickness are the square electric cell of 16 millimeters.This square electric cell is prepared into lithium ion battery, wherein uses 1.0mol/L LiPF
6/ EC+DEC(VEC:VDEC=1:1) (EC:ethylene carbonate, ethylene carbonate; DEC:diethyl carbonate, diethyl carbonate) make electrolyte, U.S. Celgard 2300 is barrier film, prepares 10AH soft bag lithium ionic cell.
Test: the adhesion of electrodes of lithium-ion batteries (the adhesion here refers to the adhesion of LiFePO4 coating layer and electrode plates, lower with) and surface resistance are tested, in adhesion peel strength be 0.38N as shown in Figure 1, surface resistance is 30m Ω; The high rate performance excellence of lithium ion battery, as shown in Figure 2,4C/0.5C is 91.9%; Test the temperature rise parameter of lithium ion battery as shown in Figure 4, battery is under 3.0C multiplying power discharging condition simultaneously, and temperature rise is 19 DEG C;
As a comparison case, in electrode plates, aluminium foil is for etching aluminium foil not with do not carry out the processing of nano-sized carbon coating, and electrolyte, barrier film and structural design thereof are identical with the present embodiment, finally prepare 10AH soft bag lithium ionic cell.In the adhesion of its pole piece of last test, peel strength is 0.075N, and surface resistance is 85m Ω; The high rate performance of battery is that 4C/0.5C is 90.1%; Battery is under 3.0C multiplying power discharging condition, and temperature rise is 25 DEG C.
Embodiment 2
The preparation method of the lithium ion battery electrode piece of the present embodiment, comprises the steps:
1) by red fuming nitric acid (RFNA) etching aluminium foil, make its aluminium foil etch the etching aluminium foil that groove thickness is 0.5 μ m, groove is along the horizontal expansion of aluminium foil, and the width of rebate of groove is 4mm, and etching aluminium foil surface density is 70g/m
2;
2) take 500 grams of aqueous binders A (binding agent is LA133 aqueous binders, Chengdu Yindile Power Source Science and Technology Co., Ltd produce), 1500 grams of second distillation aqueous solvents, carry out mechanical agitation 2 hours, obtain homogeneous, stable binder system; Under ultrasonic wave dispersion condition, divide and added powder nanometer conductive carbon combined conductive agent one time every 45 minutes three times, its conductive nano carbon combined conductive agent is 52 grams of nano carbon blacks (granularity 1nm) and 13 grams of Supper P combined conductive agent (granularity 1nm; Producer: Te Migao company of Switzerland produces) composition, after adding, disperse 3 hours at ultrasonic echography again, finally obtain coating liquid, the viscosity of coating liquid is 7000mPas; Adopt afterwards intaglio printing technology that coating liquid is coated on etching aluminium foil, coating thickness is 1 μ m, after being dried, obtains lithium ion battery electrode piece.
Adopt the lithium ion battery electrode piece of the present embodiment to be prepared into lithium ion battery, this lithium ion battery and preparation method are with embodiment 1.
Test: the adhesion of electrodes of lithium-ion batteries and surface resistance test, in adhesion, peel strength is 0.34N, surface resistance is 32m Ω; The high rate performance excellence of lithium ion battery, 4C/0.5C is 90.1%; Test the temperature rise parameter of lithium ion battery, battery is under 3.0C multiplying power discharging condition simultaneously, and temperature rise is 20.3 DEG C;
As a comparison case, in electrode plates, aluminium foil is for etching aluminium foil not with do not carry out the processing of nano-sized carbon coating, and electrolyte, barrier film and structural design thereof are identical with the present embodiment, finally prepare 10AH soft bag lithium ionic cell.In the adhesion of its pole piece of last test, peel strength is 0.075N, and surface resistance is 85m Ω; The high rate performance of battery is that 4C/0.5C is 90.1%; Battery is under 3.0C multiplying power discharging condition, and temperature rise is 25 DEG C.
Embodiment 3
The preparation method of the lithium ion battery electrode piece of the present embodiment, comprises the steps:
1) by sulfuric acid etching aluminium foil, make its aluminium foil etch the etching aluminium foil that groove thickness is 0.1 μ m, groove is along the longitudinal extension of aluminium foil, and the width of rebate of groove is 10mm, and etching aluminium foil surface density is 85g/m
2;
2) take 140 grams of aqueous binders A (binding agent is LA135 aqueous binders, Chengdu Yindile Power Source Science and Technology Co., Ltd produce), 800 grams of second distillation aqueous solvents, carry out mechanical agitation 2 hours, obtain homogeneous, stable binder system; Under ultrasonic wave dispersion condition, divide and added powder nanometer conductive carbon combined conductive agent one time every 60 minutes three times, its conductive nano carbon combined conductive agent is 45 grams of nano carbon blacks (granularity 100nm), after adding, disperse 5 hours at ultrasonic echography again, finally obtain coating liquid, the viscosity of coating liquid is 7000mPas; Adopt afterwards intaglio printing technology that coating liquid is coated on etching aluminium foil, coating thickness is 5 μ m, after being dried, obtains lithium ion battery electrode piece.
Adopt the lithium ion battery electrode piece of the present embodiment to be prepared into lithium ion battery, this lithium ion battery and preparation method are with embodiment 1.
Test: the test of the adhesion of electrodes of lithium-ion batteries and surface resistance, in adhesion peel strength be 0.31N as shown in Figure 1, surface resistance is 36m Ω; The high rate performance excellence of lithium ion battery, 4C/0.5C is 90.1%; Test the temperature rise parameter of lithium ion battery, battery is under 3.0C multiplying power discharging condition simultaneously, and temperature rise is 21.2 DEG C;
As a comparison case, in electrode plates, aluminium foil is for etching aluminium foil not with do not carry out the processing of nano-sized carbon coating, and electrolyte, barrier film and structural design thereof are identical with the present embodiment, finally prepare 10AH soft bag lithium ionic cell.In the adhesion of its pole piece of last test, peel strength is 0.075N, and surface resistance is 85m Ω; The high rate performance of battery is that 4C/0.5C is 90.1%; Battery is under 3.0C multiplying power discharging condition, and temperature rise is 25 DEG C.
Claims (8)
1. a preparation method for lithium ion battery electrode piece, is characterized in that: comprise the following steps:
1) get aluminium foil, adopt oxidizing acid to etch the groove that thickness is 0.1～1 μ m on aluminium foil surface, after etching, the surface density of aluminium foil is 60～85g/m
2;
2) in surface-coated one deck nano-sized carbon coating of aluminium foil etched recesses, make lithium ion battery electrode piece, the thickness of this Nano carbon coating is 1～5 μ m;
Described groove is horizontal or longitudinal extension along aluminium foil, and its width of rebate is 0.1～10mm.
2. the preparation method of lithium ion battery electrode piece according to claim 1, is characterized in that: step 1) described oxidizing acid is nitric acid or sulfuric acid.
3. the preparation method of lithium ion battery electrode piece according to claim 1, is characterized in that: described nano-sized carbon coating comprises carbon nano-particles.
4. the preparation method of lithium ion battery electrode piece according to claim 1, it is characterized in that: step 2) coating of described nano-sized carbon coating adopts with the following method: 140～500 parts of aqueous binders, 800～1500 parts of redistilled water mixing and stirring are obtained to binder system, under ultrasonic wave dispersion condition, in binder system, add 45～65 parts of carbon nano-particles, after adding, continue ultrasonic wave and disperse within 1～5 hour, to obtain coating liquid, this coating liquid is coated in uniformly to the surface of aluminium foil etched recesses.
5. the preparation method of lithium ion battery electrode piece according to claim 4, is characterized in that: described carbon nano-particle divides three times and adds above, and the time interval adding is 30～60 minutes.
6. according to the preparation method of the lithium ion battery electrode piece described in claim 3 or 4, it is characterized in that: described carbon nano-particles be one or both in carbon black, Supper P combined conductive agent arbitrarily than mixing, the granularity of described carbon nano-particles is 1～100nm.
7. the preparation method of lithium ion battery electrode piece according to claim 4, is characterized in that: described aqueous binders is that one or both of polypropylene, poly-propionic acid are arbitrarily than mixing.
8. the preparation method of lithium ion battery electrode piece according to claim 4, is characterized in that: the surface that coating liquid is coated in aluminium foil etched recesses uniformly adopts intaglio printing technology to apply.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210273175.0A CN102769122B (en) | 2012-07-31 | 2012-07-31 | Method for preparing electrode plate of lithium ion battery |
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| CN201210273175.0A CN102769122B (en) | 2012-07-31 | 2012-07-31 | Method for preparing electrode plate of lithium ion battery |
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| CN102769122B true CN102769122B (en) | 2014-10-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024030913A1 (en) * | 2022-08-02 | 2024-02-08 | 24M Technologies, Inc. | Systems, devices, and methods for providing heat to electrochemical cells and electrochemical cell stacks |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104821400B (en) * | 2015-03-18 | 2017-01-25 | 江苏乐能电池股份有限公司 | Safe conductive liquid for lithium iron phosphate and preparation method thereof |
| CN106784603A (en) * | 2016-12-28 | 2017-05-31 | 珠海银隆新能源有限公司 | A kind of preparation method of current collector coatings |
| CN110492059B (en) * | 2019-08-28 | 2022-10-25 | 湖北锂诺新能源科技有限公司 | Preparation method of lithium ion battery with high-heat-dissipation pole piece |
| CN112599780A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院过程工程研究所 | Method for modifying surface of current collector of lithium slurry battery |
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| CN201927671U (en) * | 2011-01-07 | 2011-08-10 | 湖南华慧新能源有限公司 | Pole piece of positive pole of lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4599070B2 (en) * | 2004-03-17 | 2010-12-15 | 株式会社東芝 | Nonaqueous electrolyte secondary battery |
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| CN101174509A (en) * | 2007-10-25 | 2008-05-07 | 宁波富达电器有限公司 | Collecting electrode used in super capacitor and its surface treating method |
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| WO2024030913A1 (en) * | 2022-08-02 | 2024-02-08 | 24M Technologies, Inc. | Systems, devices, and methods for providing heat to electrochemical cells and electrochemical cell stacks |
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